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Acta Crystallogr Sect E Struct Rep Online. 2009 July 1; 65(Pt 7): o1615.
Published online 2009 June 20. doi:  10.1107/S1600536809022582
PMCID: PMC2969271

4-Methyl-3-nitro­pyridin-2-amine

Abstract

In the title compound, C6H7N3O2, the dihedral angle between the nitro group and the pyridine ring is 15.5 (3)° and an intra­molecular N—H(...)O hydrogen bond occurs. In the crystal, inversion dimers linked by two N—H(...)N hydrogen bonds occur, resulting in R 2 2(8) rings. The packing is stabilized by aromatic π–π stacking [centroid–centroid distance = 3.5666 (15) Å] and a short N—O(...)π contact is seen.

Related literature

For a related structure, see: Kvick & Noordik (1977 [triangle]). For graph-set notation, see: Bernstein et al. (1995 [triangle]).

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Object name is e-65-o1615-scheme1.jpg

Experimental

Crystal data

  • C6H7N3O2
  • M r = 153.15
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1615-efi1.jpg
  • a = 7.3776 (6) Å
  • b = 12.8673 (11) Å
  • c = 7.3884 (6) Å
  • β = 104.364 (4)°
  • V = 679.45 (10) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.12 mm−1
  • T = 296 K
  • 0.25 × 0.10 × 0.08 mm

Data collection

  • Bruker Kappa APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.985, T max = 0.992
  • 7483 measured reflections
  • 1677 independent reflections
  • 759 reflections with I > 2σ(I)
  • R int = 0.055

Refinement

  • R[F 2 > 2σ(F 2)] = 0.056
  • wR(F 2) = 0.173
  • S = 1.00
  • 1677 reflections
  • 107 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.39 e Å−3
  • Δρmin = −0.32 e Å−3

Data collection: APEX2 (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]) and PLATON (Spek, 2009 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]) and PLATON.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809022582/hb5007sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809022582/hb5007Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors acknowledge the Higher Education Commission, Islamabad, Pakistan, and Bana International, Karachi, Pakistan, for funding the purchase of the diffractometer at GCU, Lahore and for technical support, respectively.

supplementary crystallographic information

Comment

Pyridines form a very important class of heterocyclic compounds. In it are included various vitamins, enzymes, pharmaceuticals, dyes, agrochemicals and other products. The title compound (I), (Fig. 1) is nitro substituted 2-Amino-4-methylpyridine.

The crystal structure of (II) 2-Amino-4-methylpyridine (Kvick & Noordik, 1977) has been reported. In (I), the pyridine ring A (C1—C5/N1) is planar with Rms deviation of 0.0135 Å. The amino N-atom and the methyl C-atom deviates from the plane of ring A by -0.0551 (37) Å and -0.044 (4) Å, respectively. The dihedral angle between ring A and nitro group B (O1/N3/O2) is 15.53 (27)°. The title compound consists of dimers due to inversion related intermolecular H-bonds of N–H···N type forming ring motifs R22(8) (Bernstein et al., 1995). The interamoleculr H-bond of N–H···O type completes R11(6) ring motif (Fig. 2). The molecules are stabilized due to π–π-interactions with centroid to centroid distance of 3.5666 (15) Å [CgA···CgAi: symmetry code i = 2 - x, -y, -z] and N–O···π interactions (Table 1).

Experimental

2-Amino-4-picoline (1.1 g, 0.01 mol) was dissolved in 10 ml of concentrated nitric and sulfuric acid (1:1) and cooled to 278 K. The mixture was left overnight and the resultant nitramino product was further treated with 5 ml of conc. sulfuric acid at room temperature for 3 h and poured over 250 g of crushed ice. The precipitates obtained were collected by filtration and subjected to steam distillation. The title compound was obtained as yellow needles of (I) on cooling the distillate to room temperature.

Refinement

The coordinates of the H-atoms of the NH2 group were located in a difference map and refined. The other H-atoms were positioned geometrically (C—H = 0.93—0.96 Å) and refined as riding with Uiso(H) = 1.2Ueq(C, N).

Figures

Fig. 1.
View of (I) with displacement ellipsoids drawn at the 50% probability level. H-atoms are shown by small spheres of arbitrary radii. Intermolecular H-bond is shown by dotted lines.
Fig. 2.
The partial packing of (I), which shows that molecules form dimers.

Crystal data

C6H7N3O2F(000) = 320
Mr = 153.15Dx = 1.497 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1677 reflections
a = 7.3776 (6) Åθ = 3.2–28.3°
b = 12.8673 (11) ŵ = 0.12 mm1
c = 7.3884 (6) ÅT = 296 K
β = 104.364 (4)°Needle, yellow
V = 679.45 (10) Å30.25 × 0.10 × 0.08 mm
Z = 4

Data collection

Bruker Kappa APEXII CCD diffractometer1677 independent reflections
Radiation source: fine-focus sealed tube759 reflections with I > 2σ(I)
graphiteRint = 0.055
Detector resolution: 7.40 pixels mm-1θmax = 28.3°, θmin = 3.2°
ω scansh = −9→9
Absorption correction: multi-scan (SADABS; Bruker, 2005)k = −17→17
Tmin = 0.985, Tmax = 0.992l = −9→9
7483 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.056Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.173H atoms treated by a mixture of independent and constrained refinement
S = 1.00w = 1/[σ2(Fo2) + (0.0745P)2 + 0.0769P] where P = (Fo2 + 2Fc2)/3
1677 reflections(Δ/σ)max < 0.001
107 parametersΔρmax = 0.39 e Å3
0 restraintsΔρmin = −0.31 e Å3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
O10.9915 (3)−0.20091 (18)0.2978 (3)0.0860 (10)
O21.2249 (3)−0.11801 (19)0.4483 (4)0.0904 (10)
N10.7197 (3)0.06783 (18)0.0831 (3)0.0426 (8)
N20.6845 (4)−0.1039 (2)0.1310 (3)0.0529 (9)
N31.0759 (3)−0.11908 (19)0.3358 (3)0.0475 (9)
C10.8004 (4)−0.0221 (2)0.1552 (3)0.0386 (8)
C20.9935 (3)−0.0238 (2)0.2507 (3)0.0378 (9)
C31.1041 (3)0.0656 (2)0.2608 (3)0.0405 (9)
C41.0135 (4)0.1542 (2)0.1803 (4)0.0480 (10)
C50.8246 (4)0.1511 (2)0.0979 (4)0.0472 (10)
C61.3108 (4)0.0719 (3)0.3480 (4)0.0555 (10)
H2A0.570 (5)−0.089 (2)0.066 (4)0.0635*
H2B0.730 (4)−0.164 (2)0.156 (4)0.0635*
H41.079860.215820.181700.0576*
H50.767020.212750.048990.0566*
H6A1.357380.137850.318880.0666*
H6B1.373650.017080.299730.0666*
H6C1.333340.064750.481070.0666*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0667 (16)0.0497 (16)0.127 (2)−0.0025 (12)−0.0035 (14)0.0240 (14)
O20.0609 (15)0.0759 (19)0.110 (2)0.0105 (13)−0.0247 (14)0.0200 (14)
N10.0373 (12)0.0424 (14)0.0475 (13)0.0041 (11)0.0096 (10)−0.0006 (11)
N20.0399 (13)0.0506 (17)0.0639 (16)−0.0020 (13)0.0048 (12)0.0097 (14)
N30.0416 (14)0.0502 (17)0.0506 (14)0.0091 (12)0.0110 (12)0.0076 (12)
C10.0355 (14)0.0427 (16)0.0394 (14)0.0019 (13)0.0126 (11)−0.0016 (12)
C20.0356 (15)0.0404 (16)0.0378 (14)0.0070 (12)0.0101 (11)0.0004 (12)
C30.0361 (14)0.0500 (18)0.0354 (14)0.0038 (13)0.0090 (11)−0.0046 (12)
C40.0493 (18)0.0399 (17)0.0547 (17)−0.0042 (14)0.0126 (14)−0.0032 (14)
C50.0495 (18)0.0421 (17)0.0492 (16)0.0105 (14)0.0110 (13)−0.0001 (13)
C60.0391 (16)0.066 (2)0.0589 (18)−0.0051 (14)0.0077 (13)−0.0058 (16)

Geometric parameters (Å, °)

O1—N31.220 (3)C2—C31.402 (4)
O2—N31.203 (3)C3—C41.380 (4)
N1—C11.349 (3)C3—C61.503 (4)
N1—C51.310 (4)C4—C51.376 (4)
N2—C11.340 (4)C4—H40.9300
N3—C21.442 (3)C5—H50.9300
N2—H2B0.85 (3)C6—H6A0.9600
N2—H2A0.88 (3)C6—H6B0.9600
C1—C21.425 (4)C6—H6C0.9600
C1—N1—C5118.4 (2)C2—C3—C4116.2 (2)
O1—N3—O2119.7 (2)C4—C3—C6118.2 (3)
O1—N3—C2119.9 (2)C3—C4—C5119.7 (2)
O2—N3—C2120.4 (2)N1—C5—C4125.0 (3)
H2A—N2—H2B126 (3)C3—C4—H4120.00
C1—N2—H2A113.3 (18)C5—C4—H4120.00
C1—N2—H2B119 (2)N1—C5—H5118.00
N1—C1—N2114.6 (3)C4—C5—H5118.00
N1—C1—C2119.9 (2)C3—C6—H6A109.00
N2—C1—C2125.5 (2)C3—C6—H6B109.00
N3—C2—C1119.4 (2)C3—C6—H6C109.00
N3—C2—C3119.9 (2)H6A—C6—H6B109.00
C1—C2—C3120.8 (2)H6A—C6—H6C109.00
C2—C3—C6125.6 (2)H6B—C6—H6C109.00
C5—N1—C1—N2−178.7 (2)N2—C1—C2—N3−2.1 (4)
C5—N1—C1—C22.3 (4)N2—C1—C2—C3177.2 (2)
C1—N1—C5—C40.8 (4)N3—C2—C3—C4−178.3 (2)
O1—N3—C2—C113.3 (3)N3—C2—C3—C62.8 (4)
O1—N3—C2—C3−166.0 (2)C1—C2—C3—C42.4 (3)
O2—N3—C2—C1−164.5 (2)C1—C2—C3—C6−176.4 (2)
O2—N3—C2—C316.2 (4)C2—C3—C4—C50.5 (4)
N1—C1—C2—N3176.7 (2)C6—C3—C4—C5179.5 (3)
N1—C1—C2—C3−4.0 (3)C3—C4—C5—N1−2.3 (5)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2A···N1i0.88 (3)2.17 (4)3.045 (4)174 (3)
N2—H2B···O10.85 (3)2.01 (3)2.612 (4)127 (2)
N3—O2···Cg1ii1.203 (3)3.2743 (3)3.681 (12)100.16 (17)

Symmetry codes: (i) −x+1, −y, −z; (ii) −x+2, −y, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5007).

References

  • Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl.34, 1555–1573.
  • Bruker (2005). SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2007). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Kvick, Å. & Noordik, J. (1977). Acta Cryst. B33, 2862–2866.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]

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